1,1,1-trifluoro-3-[(R)-(4-methylphenyl)sulfinyl]propan-2-one | 113965-64-3

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: 1,1,1-trifluoro-3-[(R)-(4-methylphenyl)sulfinyl]propan-2-one
• CAS: 113965-64-3
• 化学式: C₁₀H₉F₃O₂S
• 分子量: 250.241
• InChiKey: JKLIFQWMWWWYLO-MRXNPFEDSA-N

物化性质

• 沸点：
  332.2±42.0 °C(Predicted)
• 密度：
  1.39±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.4
• 重原子数：
  16
• 可旋转键数：
  3
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.3
• 拓扑面积：
  53.4
• 氢给体数：
  0
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  1,1,1-trifluoro-3-[(R)-(4-methylphenyl)sulfinyl]propan-2-one 在 正丁基锂 作用下， 以 甲苯 、 苯 为溶剂， 反应 0.33h， 生成 benzyl N-[(Z)-3,3,3-trifluoro-1-[(R)-(4-methylphenyl)sulfinyl]prop-1-en-2-yl]carbamate
  参考文献：
  名称：

  New Versatile Fluorinated Chiral Building Blocks:  Synthesis and Reactivity of Optically Pure α-(Fluoroalkyl)-β-sulfinylenamines

  摘要：

  Efficient synthesis of optically pure alpha-(fluoroalkyl)-beta-sulfinyl enamines has been achieved by aza-Wittig reaction of triphenyliminophosphoranes with the corresponding alpha-fluorinated-alpha'-sulfinyl ketones. The title compounds 3,4 showed an overwhelming preference for the Z stereochemistry of the enamine form. Their general reactivity has been studied. The reaction with some electrophiles (i.e. benzyl chloroformate and benzyl and allyl bromide) occurs at the nitrogen atom providing the corresponding N,N-disubstituted enamines. Nucleophiles add smoothly to C-2: heteroatom-centered nucleophiles like methanol, ammonia, and thiophenol afford gem-disubstituted derivatives under thermodynamic control, while a C-centered nucleophile like nitromethane adds in irreversible fashion. The hydride- and deuteride-promoted reduction of 3,4 to the N-Cbz-protected (14) and N-unprotected (15) alpha-fluorinated-alpha'-sulfinyl amines has been studied. Hydride addition was stereoselective, while low stereoselection was obtained with the other tested nucleophiles. Desulfurization of the optically pure 1,1,1-trifluoro-3-sulfinyl amine 15a afforded (R)-1-(trifluoromethyl)ethylamine 17. The Pummerer rearrangement of 14 occurs in an unusual nonoxidative way affording the sulfenamide 24, that readily provided (R)-(2-H)- and -(2-D)-3,3,3-trifluoroalaninol (19) and (R)-3,3,3-trifluoroalanine (22).

  DOI：

  10.1021/jo952097r
• 作为产物：
  描述：

  三氟乙酸乙酯 、 (R)-(+)-甲基对甲苯砜 在 lithium diisopropyl amide 作用下， 以 四氢呋喃 为溶剂， 以90%的产率得到1,1,1-trifluoro-3-[(R)-(4-methylphenyl)sulfinyl]propan-2-one
  参考文献：
  名称：

  采用（R ; E）-3,3,3-三氟丙-1-烯基对甲苯基亚砜的高度立体选择性不对称迈克尔加成反应

  摘要：

  由三氟乙酸乙酯分三步制备的（R；E）-3,3,3-三氟丙-1-烯基对甲苯基亚砜在与烯醇盐的迈克尔加成反应中显示出高度的非对映选择性；通过这种方式，可以容易地以高收率和高光学纯度获得光学活性的三氟甲基化的有机分子。

  DOI：

  10.1039/c39870001340

文献信息

• Synthesis of (<i>R</i>c,<i>S</i>s)-1,1,1-Trifluoro-3-(<i>p</i>-tolylsulfinyl)-2-propanol by an Asymmetric Reduction with a Yeast,<i>Yamadazyma farinosa</i>, as a Key-step
  作者：Atsushi Sakai、Mikio Bakke、Hiromichi Ohta、Hiroshi Kosugi、Takeshi Sugai

  DOI：10.1246/cl.1999.1255

  日期：1999.11

  (>99% e.e.), an important reagent for the asymmetric protonation of substituted enolates, was prepared (70%) from (S)-methyl p-tolyl sulfoxide. The stereoselectivity of the Yamdazyma farinosa-catalyzed reduction of carbonyl groups, the key step for the introduction of an asymmetric carbon, was greatly affected by the stereochemistry of the asymmetric sulfur atom. The reduction of (S)-1,1,1-trifluor

  (Rc,Ss)-1,1,1-trifluoro-3-(p-tolylsulfinyl)-2-propanol (>99% ee)，一种用于取代烯醇不对称质子化的重要试剂，由 (70%) 制备(S)-甲基对甲苯基亚砜。Yamdazyma farinosa 催化的羰基还原是引入不对称碳的关键步骤，其立体选择性受不对称硫原子的立体化学影响很大。(S)-1,1,1-三氟-3-(对甲苯基亚磺酰基)-2-丙酮的还原以相当立体选择性的方式顺利进行，得到所需化合物，而 (Rc, Rs)-和(Sc,Rs)-异构体是从具有相反(R)-构型的底物获得的。
• Homochiral Perfluoroalkyl-Group-Substituted Secondary Alcohols Through Stereoselective Reduction of Perfluoroalkyl 1-(<i>p</i>-Tolylsulfinyl)alkyl Ketones
  作者：Pierfrancesco Bravo、Massimo Frigerio、Giuseppe Resnati

  DOI：10.1055/s-1988-27764

  日期：——

  The reduction of some enantiomerically pure perfluoroalkyl α-(p-tolylsulfinyl) ketones was performed. Alcohols containing perfluoroalkyl and p-tolylsulfinyl groups were obtained with high diastereoselection when a phenyl residue was present on the sulfinylated carbon and with lower diastereoselection in the other cases. Removal of the chiral sulfinyl group from single diastereoisomers gave secondary alcohols containing a perfluoroalkyl group in enantiomerically pure form.

  对某些对映纯的全氟烷基 α-(对甲苯亚磺酰基)酮进行了还原。当亚磺酰基碳上存在苯基残基时，含有全氟烷基和对甲苯亚磺酰基的醇类具有高立体选择性，而在其他情况下具有较低立体选择性。从单一非对映异构体中去除手性亚磺酰基，得到含有全氟烷基的对映纯的仲醇。
• Two Practical and Efficient Approaches to Fluorinated and Nonfluorinated Chiral β-Imino Sulfoxides
  作者：Santos Fustero、Antonio Navarro、Belén Pina、Amparo Asensio、Pierfrancesco Bravo、Marcello Crucianelli、Alessandro Volonterio、Matteo Zanda

  DOI：10.1021/jo980336f

  日期：1998.9.1

  Reaction of fluorinated and nonfluorinated N-substituted imidoyl chlorides 1 with lithium derivatives of enantiopure methyl p-tolyl sulfoxide 2a (or racemic methyl phenyl sulfoxide 2b) gave a wi;ie variety of chiral N-substituted beta-imino sulfoxides 4 in good to excellent yields. The title compounds (R)-4 were also prepared by aza-Wittig reaction of gamma-fluoro-beta-keto sulfoxides (R)-5 and N-aryl iminophosphoranes 6. The imino-enamino equilibrium was studied, showing, in all instances, the imino form as the predominant tautomer independent of the nature of the N-substituent. The configuration of the C=N double bond was found to be Z for both N-alkyl and N-aryl derivatives on the basis of H-1 NMR NOE difference experiments performed over several compounds. Ab initio calculations (HF/6-31G*) carried out on several representative examples of 1 and 4 are, in general, consistent with the experimental results.
• Fluorinated enol ethers bearing chiral arylsulphinyl groups
  作者：Pierfrancesco Bravo、Luca Bruché、Marcello Crucianelli、Annamaria Merli

  DOI：10.1016/0022-1139(95)03262-c

  日期：1995.9

  A synthesis of 2-alkoxy-2-fluoroalkyl-1-(p-tolylsulphinyl) ethenes 4 with good regioselectivity from gamma-fluorosubstituted beta-ketosulphoxides 3 is described
• Mild α-fluorination of enantiomerically pure β-ketosulfoxides by F-TEDA-BF4
  作者：Alberto Arnone、Pierfrancesco Bravo、Massimo Frigerio、Giuliana Salani、Fiorenza Viani、Matteo Zanda、Carmela Zappalà

  DOI：10.1016/s0022-1139(97)00035-3

  日期：1997.8

  A wide range of cu-sodium derivatives of chiral and enantiomerically pure beta-ketosulfoxides have been regioselectively fluorinated with the 'F+' fluorinating agent F-TEDA-BF4 without affecting the sulfinyl stereogenic center. alpha-Monofluoro-beta-ketosulfoxides produced in this reaction can undergo further fluorination providing the corresponding alpha,alpha-difluoro derivatives, easily transformed by deacylation into enantiomerically pure (S)-difluoromethyl-p-tolylsulfoxide. (C) 1997 Elsevier Science S.A.